Toxic material



Patented Nov. 21, 1944 TOXIC MATERIAL Jacquelin E. Harvey, Jr., Washington, D. 0., and RobertlL White, Jr., and Joseph A. Vaughan,

Atlanta, G

assignors of one-half to said I Harvey, Jr... and one-half to Southern Wood Preserving OompaimEast Point, Ga, a corporation of Georgia No, Dra

wing. Original application November 10,

1942, Serial No. 465,166. Divided and this appiioation November 23, 1943, SerialNo. 511,482

a 4 Claims. (01. 196-149) The instant invention relates to theproduction' of toxicfoils 'employable. as fungicides, insecticides, and for any other service to which toxic oils may be put, being a division of our applicatiOn Serial No. 465,168, filed November 10, 1942,,

for Method of producing useful products. and products thereof. Y

More especially the instant invention relates to the productionof toxic oils from'mixtures of petroleum fractions characterized by ring structure content. Among such. starting materials may be mentioned mixtures of petroleum fractions characterized by rinpstructure content recovered from petroleum fractions by well known extraction methodsincluding extractive distillationed mixtures of petroleum fractions characterized by ring structure content as flowing from tions having ringstructures induced in thecourse of thermal and/or catalytic treatment, as for example having ring structuresinduced in the course of one or more thermal, and/or catalytic treatments of unusual length,.as for example, for D riods of from lhours or more. i

An object of'the instant invention is the. productionof toxic oils from the aforenamed petroleum fractions or others whereby to provide oils of the preservative type, as for example preservative wood impregnants conforming-to speciflcations extant or acceptable to the trade consuming such oil materials.

Another object of the instant invention is the provision of preservative wood impregnants haw ing boiling ranges and residues in accordance with published specifications and/or in accordance with consu'merpreference.

Another object of the instant invention is thev unveiling of latent toxicity in mixtures of petroleum fractions havinfg inherent but inhibited toxicity. 7

Another object maintenance of a preponderant proportion of the cyclic structures in the material undergoing induction in at. least a methylated condition, it having been found that objectionable reaction of the instant invention is the products are formed if this obiect is not to Another object of the inventionis the control of saturatesinspecific fractions of the material undergoing treatment.

Still another object of theinstant invention is the control of the percentage of cyclic structures,

1 as for instance aromatics. in specific fractions of tion and az'eotropic distillation. Also maybe menthe beneficiated material which is characterized by induced toxic properties.

Yet. another object of the instant invention is the provision in the overall beneficiated materlal of that percentage of newly induced fractions boiling below 210 C. which is conducive to the induction of toxicity in other fractions of the material under treatment.

Another object of the instant invention is a change inspecific gravity in the overall benefithermal and/or catalytic treatment. of certainpe- 'troleum fractions which includes petroleum fracciated material which isconducive tothe induction of toxicity.

Another object of the instant invention is the coordination of processvariables so as to provide specific gravities within definite limits in various fractions of the beneficiated material.

Another object of the instantinvention is a coordination of process variables which will provide in various fractional parts of the beneficiated material cyclic structures with specific gravities falling within the limitshereinafter stated.

Another object of the instant invention is the induction of toxicity in the presence of catalytic materials adapted to favorably influence said toxicity induction. i

Another object of the instant invention is the induction of additional toxicity into fractional parts of the once beneficiat'ed starting material under specific controls of process variables. I

I In the past wood preservative oils of the ,high temperature coal tar derived type have been employed in quantities greatly exceeding the total of all other wood preservative oils. From the standpoint of availability of said coal tar as the parent product of wood preservative oils, it is annually produced in this country under normal conditions to the extent of five hundred million to six hundred million gallons. This quantity of coal is capable of yielding an amount of highly effective wood preservative oil which would make this country self-sumcient in its wood preservative requirements. However, due to the fact that when a wood preservative distillate (creosote) is recovered from coal tar there remains in the still a residue (pitch) which, at best, is a low priced product and which, at worst, is a seriously distress product to the end that at 2 2,303,244 i times it is placed in inventory rather than sold. Sol. in CS 99.8 The current method of processing coal tar leaves Loss 50 grams, 5 hours, 325 F 8.9 much to be desired. The net result of this sit- Residueof 100 pene per cent-.. 37.5 uation obtaining is that the coal tar distiller A. S. T.'M. distillation: I usually confines himself to that distillation re- I. B. P F 518 covery of creosote which would correspond to rec, F 565 the attending amount of pitch that he can marrec. "F 589 ket at a profit. Accordingly, over a period of, 30% rec. F 614 years several hundred million gallons of creosote 40% rec. F 637 oil have been imported into this country. That 10 50% rec. F 660 such a situation should obtain is apparently a p 60% rec. "F 1 75 paradox in that we annually produce a quantity T of high temperature coal tar which if processed In the. foregoing tabular data P. M. C. C. means to yield creosote would make 115 self sumcient in Pensky-Martin Closed Cup; C. 0. C. means Cleveland that requirement. A survey of this paradox is 15 Open fully outlined in an address given by no less an Upon v ting the foregoing oil for its toxauthority than S. P. Miller, technical director, icity to Wood destroying fungi ad 5 it The tt c 40 Rector st t w was found that this 011 did not inhibit the growth York city, before the Franklin Institute, Phila-- of e u named at a concentration of p to delphia, Pennsylvania in December, 1932. The 720 and including 1 1 economics of coal tar hav t materially It is now discovered that the oil above named changed since that dat or other 'oils of cyclic content produced by the In .view of the apparent inability of the coal P um in u y can e increased in i y tar industry to provide national needs of w od in accordance with the process of the instant preservative oils, a strong incentive is given to ion. groups'processing other types of oil t invad According to the instant invention oils of the lucrative wood preservative market. At the cyclic content Produced y the Petroleum u present time many types of aromatic oils are are reformed, a r d. ed nd/0 produced by the petroleum industry, and the converted to oils of a. more toxic nature havin high boiling oils of aromatic content produced characteristics pt e to consumers of wood by this industry have for several years been testpreservative impregmmt /0 60111011111118 t0 ed for their wood preservative emciency. Wood preservative Specifications ta t.

By the term petroleum' aromatic as used The following examples will serve'to illustrate herein and in the appended claims is meant to several modes of practicing the present invention. include mixtures of petroleum fractions char- Eimmple mixture of petroleum fractidns acterized by cyclic content and includes speciflcharacterizedby cyclic t t d having but cglly venous form and types of naphthenes slight growth inhibition to wood destroyingfungi. found in various mixtures of petroleum fractions, as f r example the hell productlshown in the as for example monocyclic and polycyclic naphr g in tabular data, is char ed t V l thene 40 adapted to operate at superatmospheric pressure; Th soall petroleum aromatics which as for instance at a pressure as high as several eludes the monocyclic and polycyclic naphthenes hundred atmospheres h 1 s ought up to and unsaturated hydrocarbon fractions have in tempel'atllle 01 Where it iwheld in the the past been produced in very large quantiti commonly accepted liquid phase under a pressure However, very littlework'has been done on these of 750 Pmmds such a length time as to materials. Such a fact is borne out on page 667, Pmvide 20%new1y ml'med materials boning "Reactions of pure hydrocarbons Gustav Eg- 10W 1 g, Reinhold Publi hin corporation, 330 w At the end of the stated period the oil is with- 42 st t New York City, which states; drawn from the processing chamber, cooled and Despite the fact that naphthenes or cycloinspected- Upon inspection the on is found to parafllnes are available in enormous quantities, have toxic properties unveiled as the resultof' as shown by an estimate of 100,000,000 ba 1 the treatment above named, and such induction 0 present in the 1,498,000,000 barrels of crude oil 01 toxicity flows from, arming things the which was the world's production in 1934, comprovision of t named Percentage newly paratively little work of a pyrolytic nature has duced fractions boning below been performed on individual naphthene hydw In the induction of toxicity in accordance with carbons or the cycloolefinsy the instant process, it hasbeen determined that several s ofcyclic content produced by the unless at least about 10% newly formed fractions petroleum industry have been inspected for their boiling below 210 C. are induced, latent toxicity toxicity to wood destroying fungi among which is not unveiled to the desired extent. It has also may be mentioned a high boiling Oil of cyclic been determined that if e than about. 50% content produced (1940) at the wood River newly formed materials boiling below 210 C. are flnery. of the shell on Company and which has created, reactions go forward that are prejudicial the following inspection: to the induction of toxicity, as for example there .amvity 1&8 05 occurs inordinate gasiflcation, inordinate produc- Flash M. a c oF 295 tion of undesirable fugitive materials and/or Flash, C, Q fi 0 29o polymerization of high boiling fractions of the Fixed carbon per cent" starting material under treatment. 0 Po r p i t To approximate commercial operating condi B. S. 81 W. per t by volume" 1 7o tions it is preferred to so control process variables 8. U. vis. F 151 as to provide 15-35% newly formed materials 8. U. vis. 210 FF 41 polling below 210 0., and in this manner of oper- 15- 77 F--. 34.5 ation pronounced toxicity is induced. Carbon res 6,8 In the induction of toxicity in accordance with Per cent aromatics and unsaturates 82.4 76 the instant method, the process variables are.

aseaasa.

- condition, it having been found that an attempt to totally dealkylate the cyclic structuresofthe starting material results in the formation of toxicity diluents, inordinate gasiflcation' and/or the formation of substantially non-toxic materials. The expression "in at least a methylated condition refers to the number of carbon atoms in the ring appendage or appendages. fraction of the beneficiated material of induced toxic properties, as for example and especially the material boiling between 315 0. and 355 0., has a preponderant proportion of materials of cyclic structure content present in at least a methylated condition.

Conditions that are prejudicial to the maintenance of a preponderant proportion of the cyclic structures of the starting material in at least a methylated condition are excessivetemperatures and/or excessive time of treatment Temperatures that are employable in the instant process which will provide the aforenamed end result are selected between the limits of 350- 550 0., and preferably between 425-475 0., say 440 0. or 450 0. Using the preferred temperatures whilst operating at superatmospheric pressure, as for example at pressures selected between 200-2000 pounds, it will be found that when the treatment is carried on fora period of one or two hours the end product will have induced toxicity as flowing from (1) a percentage of newly formed fractions boiling below 210 C. falling between the limits of -50% and, (2) maintenance of a preponderant proportion of the cyclic Each 5. American Wood Preservers' Association a. Up to 210 0., not more than 10% 5. Up to 235 0., not more than 40% 6. American Wood Preservers Association a. Up to 210 0.. not more than 5% b. Up to 235 0., not more than 15% 7. Prussian Ry. Y

l a. Up to 150 0., not more than 3% b. Up to 200 0., not more than 10% c. Up to 235 0., not more than25%' 8. National Paint Varnish 8: Lacquer Association a. 5% at 162 C.

b. 97% at 270 C. 9. Southern pine shingle stain oil a. 5% at 137". 0. b. 95% at 257C. 10. Neville shingle stain oil a. I. B. P.) 150C. b. 5% at 205C. c. 95% at 292 C. 11. 0arbolineum- 270 0., I. B. P.

Example 2.--Referring specifically to the overall beneflciated material of induced toxic properties produced by theprocess controls of Exampie 1, it is found that the materials boiling below and above 270 C. have relatively high andlow toxicities, respectively. It is discovered that additional toxicity may be induced into the beneficiated material by subjecting same to another toxicity inducing cycle at a higher temperature than obtained in the first cycle of toxicity induction provided the retreatment yet maintains a prestructures of the starting material inat least a methylated condition.

The pressure employed in theinstant process may be autogenous due to the pressure of evolved vapors, or the pressure may be provided by any meanswell known to the art, as for example by pumping and/or valving arrangements.

The material of induced toxic properties as flowing from the process carried out under the of the oil derived type that are meeting with consumer acceptance, the following tabular data show several published specifications:

Woon .Pxasnavlirrva IMPREGNANTS Specifications 1. American Wood Preservers Association (1. Up to 210 0., not more than 5% 11. Up to 235 0., not more than 25% 2. American Wood Preservers Association a. Up to 210 0., not more than 1% b. Up to 235 0., not more than 10% 0. Up to 355 0., not less than 65% 3. American Wood Preservers Association a. Up to 235 0., not more than 1 b. Up to 300 0., not more than l6'/ 0. Up to 355 0., not less than 4. American Wood Preservers Association '11. Up to 210 0., not more than 8% 5. Up to 235 0., not more than 35% ponderant proportion of the materials of ring structure content in at least a methylatedcondition. Accordingly, the overall once beneflciated material is subjected to another toxicity inducing cycle in the liquid phase wherein the temperature is 450 C. and the pressure 750 pounds. The treatment is continued for a period of 45 minutes. The stated period isillustrative only. The retreatment period is desirably that which provides in the finally re-beneflciated material less than newly formed materials boiling below 210 0., including fixed gas or gases, based on the starting material. At the end of the stated period the retreated material is withdrawn from its treating enclosure, cooled and inspected. Upon inspection the oil is found to have toxic properties in excess of the overall once beneflciated oil and it is also determined that the finally beneficipreservative wood impregnant, or if desired a specification wood preservative insofar as boiling range is concerned may be segregated therefrom. In lieu of retreating the entirety of the once beneficiated material at a more elevated temperature only a portion thereofmay be retreated in liquid phase and certain definite toxicity increases and benefits will flow therefrom, as for instance by retreating in liquid phase only the materials of relatively low toxicity boiling above 270 C. The retreatment of the materials'boil ing above 270 0., or a portion thereof, may be eilected at the same temperature as the initial 1 treatment, or if desired at a higher temperature.

When, the materials of relatively low toxicity are retreated for toxicity induction at either of the temperatures aforenamed, the retreated. material when commingled with that portion of the startterials, only a portion thereof may be commingled provided the comminglement furnishes an oil conforming in boiling range to consumer accep- .tance or provides a comminglement from which may be segregated an oil of consumer acceptance. Example 3.Another mode of practicing the instant process whereby to induce toxicity resides in the control of saturates in the materials boiling above 270 C. in the beneficiated oil, as for example the material boiling between 270 C. and

and 53%. and 55.3% aromatics, respectively, in

the-270-3'15 C. and 315-355 C. fractions, is subjected to a liquid phase thermal treatment at a "As stated in the foregoing, it has been found: 7

that the materials boiling above 270? C .in' the beneflciated oil have a relatively low I toxicity as compared to materials boiling belowthat temperature. It is known that the unsaturates are amongst the most toxic of oil substances. However,-it is determined that if an attempt is made to provide in the beneflciated oil of induced toxic properties, the entirety of the materials'boiling above 270 C., as for example the materials boiling between 270 C. and 355 C., as unsaturates adverse reactions occur that are prejudicial to theinduction of toxicity, as for example there. occurs (1) inordinate gasification, (2) inordinate production of materials of relatively little toxicity, and/or (3) polymerized high boiling materials. I

When providing acceptable toxicity in the overall reformed, transformed, modified and/or converted oil, it has been determined that by holding the percentage of saturates in the materials boiling above 270 C., as for example in the materials boiling between 270 C. and 355 C., to less than 30% but more than 5%, and preferably not more than 10%, no operating ills such as named will occur, or if said ills do occur they are minimized.

In accordance with an illustrative control of process variables which provides induced toxic properties whilst yielding an oil having less than 30% but more than 5% saturates in the materials boiling between 270 C. and 355 C., the following operational procedure is given:

named eriod of-treatment the beneficiated oil isdischarged from its treating enclosure, cooled.

and inspected. The beneflciated oil has only 29.7% residue above 355 C. and it is determined that there is 23.3% and 12% saturates, respectively, in the 270-3l5 C. and 315-355 C. fractions. The oil has toxic properties that are more pronounced than the parent feed stock. During the course of treatment 19.2% of newly formed materials boiling below 210 C. were formed. A further inspection of the beneficiated material discloses that a preponderant proportion of the cyclic structures ofthe starting material were maintained in at least a methylated condition.

Example 4.-An oil of cyclic content produced by the petroleum industry having inherent but inhibited toxicity, and an initial boiling point of about 270 C., about 50% residue .above 355 C.

temperature of 430 C. at a pressure of 1500 pounds for a period of one hour and'45 minutes.

At the end of the named period the treated oil is withdrawn from the processing enclosure, cooled and inspected. It is found that between 15% and newly formed fractions boiling below 210 C. have been created. The residual matters above 355 C. have been reduced by about 50%.

The fractions 270-315" C. and 315-355 C. have 72.7% and 82.7%aromatics, respectively; The overall material is characterized by toxic proper-- ties more pronounced than the starting material.

It is well understood in the'art that the aromatics, as for example aromatics having side chains not greater than the propyl group, are amongst the most toxic of oil-substances. As

stated in the foregoing the. feedstock in thev Y instant example has slightly more than 50% aromatics in the 270-355 C. fraction. However, the aromatics present. due to their peculiar type, exhibit inhibited toxicity. It would then, there fore, appear reasonable to attempt to provide in .the finally beneficiated oil total aromaticity in the materials boiling between 270C. and 335 c,

in order to induce toxicity'of a high order, and

- more especially itwould appear reasonable to attempt to provide total aromaticity of a type exhibiting satisfactory toxic values. It is discovered, however, that ifan attempt is made to provide in the beneficiated material the entirety of the materials boiling above 270 C., as for example the materials boiling between 270 C. and

355C, as aromatics, either of the toxicityinhibited or toxicity-uninhibited type, adverse reactions occur which are prejudicial to a satisfactory induction of toxicity, as for example there occurs 1) inordinate gasiflcation, (2) inordinate production of materials of relatively low toxicity, and/or (3) high boiling polymerized materials.

It is found that by holding the percentage of aromatics in the materials boiling above 270 C. in the benefioiated oil, as for example the beneficiated materials boiling between 270 C. and 355 C., to more than but less than 95%, and preferably not less than 90%, toxicity is induced in a commercial manner whilst relatively nontoxic aromatics are converted to more toxic aromatics with the added benefits that the oper- The oil of the instant example, as stated in the foregoing, has toxic properties more pronounced than the parent feed stock and may be used in f toto as a wood preservative impregnant. How" ever, thisphase of the instant invention, in any and all examples, resides in the novel manner of inducing toxic properties without reference to the provision of specification oils. However, as also v previously mentioned, specification oils may be segregated from the overall beneficiation.

Example 5;Another mode of practicing the instant process resides in controlling the specific gravity of the overall beneflciated material reaseaaca maining finally liquid after the completion of impressed process variables.

It has been found that if an oil mentioned in the foregoing characterized by inherent but in: hibited toxicity is subjected to thermal conditions whereby to provide a beneficiated material finally remaining liquid having, as compared to the parent feed stock, an overall change in specific gravity between 0.015-0.15, and preferably between 0.020-0.10, the material of the changed specific gravity has toxic properties more pronounced than the parent feed stock. This change in specific gravity is a valid test for induced toxicity.

The noted change in specific gravity which is conducive to the induction of toxic properties may be either up or down, as more fully disclosed and explained in the following:-

An oil of induced cyclic structures. produced by the petroleum industry having a specific gravity of 0.968, characterized by inherent but inhibited toxicity, boiling preponderantly above 315 C. and with substantial residual matter above 355 C. is subjected to a liquid phase thermal treatment at a temperature of 435 C. whilst under a pressure of 1,000 pounds for a period of two hours. At the end of the named treatment period the oil iscooled and inspected and found to have a specific gravity of 0.945 or a reduction in specific gravity of 0.023%. The overall beneficiated material has induced toxic properties and more than but less than 50% newly formed fractions boiling below 210 C.

According to this specific mode of operational controls and test in the instant example, the

process variables are so coordinated as to cause a reduction in specific gravity falling between the limits of 0.015 and 0.15%, and preferably between 0.020% and 0.10%. Such astated change in specific gravity has the effect of inducing and indicating the induction of toxic properties into materials previously having inhibited toxic values. The lowering of the specific gravity in the beneficiated material within the defines stated is critical within limits. Unless the overall specific gravity of the material under treat:

.ment is lowered by 0.015%, a certain unveiling of inhibited toxicity is sacrificed, and if the overall The oil of the stated increased specific gravity is inspected and found .to have toxic properties more pronounced than its parent feed stock.

Example 6.- -An oil containing materials of cyclic structure content produced by the petroleum industry having inherent but inhibited toxicity, boiling 17% at 315 0., and about 50% residual matter above 355 C., is charged to a high pressure autoclave and subjected to a liquid phase thermal treatment at atemperature selected between 425-475 C. whilst under a pressure of 1800 pounds for such a time as to jointly provide more than 10% but less than 50% newly formed fractions boiling below 210 C. and an overall specific gravity in fractional parts of the beneficiated material falling between the limits noted in the following'tabular data:

Fractions Low limit High limit and preferably between the limits noted below:

High limit When processing the named oil and operating at a pressure and temperature of 1800 pounds and 440 C., respectively, a period of about one and one-half hours will provide a specific gravity in fractional" parts of the beneficiated material falling between the preferred stated limits.

The overall beneficiated material is: inspected and found to have induced toxic properties as attested by the fact that it requires a smaller concentration for a given growth inhibition of wood specific gravity is lowered by more than 0.15%,

inordinate gasification, production of fugitive materials of relatively low toxic value and/or polymerization will occur. To avoid or minimize these ills, and/ or others, the reduction of specific gravity is preferably held between 0.0200.10%.

In connection with the change in specific gravity of the overall starting material which results in the induction of toxicity, a modification of the process resides in raising the specific gravity of the material remaining finally liquid after impression of process variables by a percentage falling between the limits of 0.015 and 0.15, and preferably between 0.020 and 0.10.

To illustrate this modification of the instant process an oil of cyclic content produced by the petroleum industry having relatively little toxicity, as for example a flashed residuum having a specific gravity of 0.927, is subjected to a liquid phase thermal treatment at a temperature selected between the limits of 450-500" C. whilst under a pressure of 1,000 pounds for such a period as to provide an overall beneficiated material remaining finally liquid having a specific gravity of 1.019. A period of from one to three hours dependent upon the temperature selected will illustratively serve for the stated increase of specific gravity.

destroying fungi than the starting material.

The overall beneficiated oil may be used as a preservative wood impregnant, or there may be segregated therefrom an oil complying with specifications extant, as for. example an oil complying with the boiling range of a carbolineum type preservative oil, which in some instances boils almost entirely above 270 C.

The specific gravity of fractional parts of the beneficiated material noted in the foregoing are critical within limits. Unless the lower limit is approximated toxicity induction will be unsatisfactory. If the high limit is exceeded adverse reaction conditions will obtain, as for example there will occur inordinate gasification and/or production of highly polymerized and objectionable materials.

In lieu of inducing toxicity whilst providing operational control of the overall specific gravity of fractional parts of the beneficiated material as heretofore disclosed, the control may be directed to the provision of specific gravities of materials of cyclic structure content in fractional parts of the beneficiated material.

As an example, an oil of cyclic structure con- 6 A I pounds for such a length of time as to Jointly provide more than 10% but less than 50% newly formed fractions boiling below 210 C. and a specific gravity of materials of cyclic structure content in fractional parts of the beneficiated material falling between the limits noted in the When processing the named oil at a pressure and temperature of 1500 pounds and 450 C., respectively, a period of about one hour and 15 minutes will provide a specific gravity of materials of cyclic structure content in fractional parts of the beneficiated material falling between the stated preferred limits.

When the beneficiated material is inspected it is found to have toxic properties more pronounced than its parent material.

The specific gravity of materials of cyclic structure content in fractional parts of the beneficiated material noted in the foregoing are critical within limits. Unless the lower limit is approximated, toxicity induction is sacrificed. If the high limit is exceeded adverse reactions that are conducive to polymerization will occur.

Example 7.-A mixture of petroleum fractions characterized by cyclic content and having inherent but inhibited toxicity, as for example the Shell product shown in the foregoing tabular data, is charged to a vessel adapted to operate at superatmospheric pressure, as for example at a pressure as high as several hundred atmospheres. The oil is brought up to a temperature of 450 C. where it is held in liquid phase under a pressure of 2,000 pounds for such a length of time as to provide about 20% newly formed fractions boiling below 210 C.

At the start of the processing period, or at any time during said period, water gas is forced into the treating vessel. The partial pressure of the water gas may vary over wide limits, as for example it may be -50% or higher. Instead of water gas. hydrogen or a hydrogen containing gas may be employed, as for example methane or its homologues, including various refinery gases.

About an hour and 15 minutes under the stated process variables will serve to provide the stated percentage of newly formed fractions boiling below 210 C. At the end of the stated period the oil is withdrawn from the processing chamber, cooled, purged of its occluded gases, if any, and inspected. Upon inspection the oil is found to have toxic properties unveiled as the result of the treatment above named, and the unveiling of the toxicity flows from, among other things,

ment have been maintained in at least a methylated condition.

Example 8.An oil of cyclic content produced by the petroleum industry having inherent but inhibited toxicity; boiling preponderantly above 315 C. and having in excess of 45% residual matter above 355 C., is charged to an autoclave and waste refinery gases forced therein to an upper limit of 800 pounds. The starting material is then brought up to a temperature of 440 C. and held in liquid phase under the generated pressure for a period of two hours.

At the end of the named period the material is cooled and inspected and is found to have more than 10% but less than 50% newly formed fractions boiling below 210 C. It is determined that the beneficiated material requires a smaller concentration for a given growth inhibition of wood destroying fungi than the starting material. Further inspection discloses that a preponderant percentage of the materials of cyclic structure content have been maintained in at least a methylated condition.

Example 9.-A liquid sulfur dioxide extract of a mixture of high boiling petroleum fractions boiling preponderantly above 315 C. with substantial residual matter above 355 C. and characterized by inherent but inhibited toxicity, is

the presence of the water gas and the provision charged to a high pressure autoclave. Twenty percent water based on the oil is added. Carbon monoxide is pumped in to an upper limit of atmospheres. Thereafter, the contents vof the autoclave are heated to a temperature of 450 C. and held in liquid phase at that temperature for a period of one and one-half hours. At the end of the named period the treated oil is discharged, cooled, purged of its occluded gases, if any, and inspected. Inspection discloses that (l) toxicity is more pronounced than in the parent material, (2) more than 10% but less than 50% newly formed fractions boiling below 210 C. have been created, and (3) a preponderant proportion of the materials of ring structure content have been maintained in at least a methylated condition.

The percentage of water noted above is illustrative only. Varying percentages may be employed, and in like manner the pressure of the carbon monoxide may vary. The major and critical requirement is that the water be present to provide during reaction conditions available nascent hydrogen.

Example 10.A furfural extract of a mixture of high boiling petroleum fractions, said extract boiling preponderantly above 315 C., having substantial residual matter above 355 C. and inherent but inhibited toxicity is charged to a high pressure autoclave and nitrogen pumped in to an upper limit of 100 atmospheres. The contents of the autoclave are then heated to 430 C. and held in liquid phase at that temperature for a period of one and one-quarter hours. At the end of the named treatment period the beneficiatedoil is inspected and found to have induced toxic properties. It is also determined that a preponderant percentage of the materials of cyclic structure content under treatment have been maintained in at least a methylated condition.

Example 11.--Referring specifically to the overall beneficiated material of induced toxic properties produced by the process controls .of Examples 7-10 inclusive, it is found that the beneficiated materials boiling below and above 270 C. have relatively high and low toxicity, respectively. It is discovered that additional toxicity may be induced into the beneficiated material by subjecting same to another liquid phase toxicity inducing cycle in the presence of an extraneous gas at a higher temperature than obtained in the first cycle of toxicity induction provided the retreatment yet maintains a preponderant proportion of the materials of ring structure content inat least a methylated condition.

Accordingly, the overall beneflciated material characterized by induced toxic properties as flowing from thermal treatment in the presence of an extraneous gas is subjected to another liquid phase toxicity induction in the presence of an extraneous gas, as an example, but not as a restriction, hydrogen, at a temperature of 465 C. and a pressure of 1800 pounds. The treatment is illustratively continued for a period of 45 minutes. The treated material is cooled and inspected and found to have toxic properties more pronounced than the overall. once beneficiated oil, and it is determined that the finally beneficiated oil yet maintains a preponderant, proportion of the cyclic materials in at least a methylated condition.

The period of retreatment may vary over wide limits, but is preferably held at that period which provides in the retreated materials less than 50% newly formed materials boiling below 210 0. as compared to the parent feed stock.

In lieu of retreating the entirety of the once beneficiated oil in the presence of an extraneous gas at a more elevated temperature, only a portion thereof may be retreated in the liquid phase and certain definite toxicity increases and benefits will flow therefrom. 1

Another mode of inducing additional toxicity into the once beneficiated oil which has been treated in the presence of an extraneous gas is by retreating in the liquid phase in the presence of an extraneous gas only the materials of relatively low toxicity boiling above 27 C. The retreatment of the materials boiling above 270 C., or a selected portion thereof, may be effected at the-same temperature as the initial treatment, or if desired, at a higher temperature. When the materials of relatively low toxicity are retreated in the presence of an extraneous gas for toxicity induction at either of the temperatures aforenamed, the retreated material when commingled with that portion of the starting material once beneficiated will provide a comminglement having toxic properties in excess of the once treated oil. In lieu of commingling the entirety of the materials once and twice treated in the presence of an extraneous gas, only aportion thereof may be commingled provided the comminglement furnishes an oil conforming in boiling range to consumer acceptance or provides a comminglement from which may be segregated an oil of consumer acceptance.

Example 12,--A liquid sulfur dioxide extract of a mixtureof petroleum lubricating fractions boiling preponderantly above 315 C. and having more than 30% saturates in materials boiling up to 355 C., is charged to a high pressure vessel and heat treated in the liquid phase in the pres ence of hydrogen at a temperature of 455 C. whilst under a pressure of 1800 pounds for such a period as to jointly provide more than 10% but less than 50%. newly formed fractions boiling below 210 C. and less than 30% but more than 5% saturates in the materials boiling between 270 C. and 355 C. Periods of from one to two hours under the stated conditions of temperature and pressure will illustratively serve to Jointly provide the stated percentage of newly induced fractions boiling below 210 C. and the named percentage of saturates in the 270-355 C fraction.

By controlling the percentage of saturates in the named fraction as stated, toxicity is induced with the added benefit that polymerized high boiling fractions are minimized or eliminated.

The beneficiated oil may be used in toto as a wood preservative impregnant or a segregation may be secured therefrom boiling in accordance with specifications noted elsewhere herein.

Example 13.--An oil of cyclic structure content produced by the petroleum industry boiling preponderantly above 315.C., having substantial residual matter above 355 C., less than 70% aromatics in the materials boiling between 270 C. and 355 C. and inherent but inhibited toxicity is heat treated in the liquid phase in the presence of a hydrogen containing gas at a temperature and pressure of 460 C. and 1500 pounds, respectively, for such a period as to jointly provide more than 10% but less than newly formed fractions boiling below 210 C. and more than 70% but less than 95% aromatics in the materials boiling between 270 C. and 355 C. In this instance a period of one and one-halfhours will illustratively serve to provide the stated characteristics in the beneficiated material.

Upon the completion of the treating period the oil is cooled, inspected and found to have a toxicity more pronounced than the starting material and for some purposes is employable in toto as a preservative wood impregnant. As taught in the foregoing, desired segregations of the over-,'

all beneficiated material may be provided as specification impregnants.

Example 14.-An oil comparable to the Shell oil showni n the foregoing itabular data having a specific gravity of 0.965, 16% boiling at 315 C.,

47% residue above 355 C. and inherent but inhibited toxicity, is charged to a high pressure autoclave and heat treated in the liquid phase in the named specific gravity. 1

At the end of the named period the oil is cooled and inspected and found to have induced toxic properties. The overall beneficiated material is stabilized to provide a residual as an oil of the. wood preservative type characterizedby induced toxic properties boiling 2% be1ow2l0 C. and

with about 29% materials boiling above 355 C.

In the example immediately above is noted a m thod for the induction of toxicity by controlling the overall reduction in specific gravity.

When treating in the presence of 8/1! extraneous gas petroleum oils characterized by; inherent but inhibited toxicity an overall reduction. in specific gravity falling between the percentages of 0015 and 0.15 will illustratively serve ,to provide induced toxicity, however, a reduction of specific gravity falling between the limits of 0.020% and 0.10% is preferred as heretofore stated. Such a stated change in specific gravity has the effect of ,inducing toxic properties into materials previously having inhibited toxic values. The lowering of the specific gravity in the beneficiated materialwithin the defines stated is critical within limits. Unless the overall specific gravity of the material under treatment is lowered by 0.015%, a certain unveiling of toxicity is sacrificed, and if the overall specific gravity is lowered by more than 0.15%, inordinate gasification, production of fugitive materials of relatively low toxic value and/ or polymerization will occur. To avoid or minimize these ills, and/or others, the reduction of specific gravity is preferably held between 0.020 and 0.10%.

With further reference to the change in specific gravity of the raw feed stock which results in the unveiling of toxicity;a modificationof the process residesin raising the specific gravity of the material remaining finally liquid after impression of process variables by a percentage falling between the limits of 0.015 and 0.15%, and preferably between 0.020 and 0.10%.

To illustrate this modification of the instant process, an oil of cyclic content produced by the petroleum industry having relatively little toxicity, as for example a flashed residuum having a specific gravity of 0.920 is subjected to a liquid phase thermal treatment in the presence of a hydrogen containing gas at a temperature selected between the limits of 430-500 C. whilst under a pressure in excess of 500 pounds for such a period as to provide an overall beneficiated oil remaining finally liquid having a specific gravity of 1.015. A period of from one to ten hours, de: pendent upon the temperature selected, will illustratively serve for the stated increase of specific gravity.

The oil of the stated increased specific gravity is inspected and found to have toxic properties more pronounced than its parent feed stock.

Example 15.-An 011 containing materials of cyclic structure content produced by the petroleum industry, having inherent but inhibited toxicity, boiling 17% at 315 C. and about 50% residual matter above 355 C., is charged to a high pressure autoclave and subjected to a liquid phase thermal treatment in the presence of hydrogen at a temperature selected between the limits of 425-500 C. whilst under a pressure of 1800 pounds for such a time as to jointly provide more than but less than 50% newly formed fractions boiling below 210 C. and an overall specific gravity in fractional parts of the beneficiated material falling between the limits noted in the following tabular data:

Fractions Low limit High limit and preferably between the limits noted below:

When processing the named oil and operating at the stated pressure and a temperature of 460'C., a period of about one and one-half hours will provide aspecific gravity in fractional parts of the beneficiated oil falling between the preferred limits and the stated percenta e of newly formed materials boiling below 210 C.

The overall beneficiated oil is inspected and found to have unveiled toxic properties as shown by the fact that'it requires a smaller concentration for a given growth inhibition of wood de stroying fungi than the parent feed stock.

The entirety of the beneficiated material may be used as a preservative wood impregnant, or there may be segregated therefrom an oil complying in boiling range with published specifications, consumer preference or acceptance.

The specific gravity defines of overall fractional parts of the beneficiated oil of induced toxic properties noted in the foregoing tabular data are criticalwithin limits. Unless the lower limit is approximated, possible unveiling of toxicity will be sacrificed. If the high limit is exceeded adverse reactions will obtain, as for example there will occur inordinate gasification, inordinate production of fugitive materials of relatively low toxic value and/or production of highly polymerized and objectionable materials.

Instead of inducing toxicity whilst providing operational control of overall fractional parts of the beneficiated material as heretofore disclosed, the operational control may be directed to the specific gravities of materials of cyclic structure content, as for example aromatics, in fractional parts of the beneficiated oil.

To illustrate this mode of operational @ntrcl, an oil of cyclic structure content produced by the petroleum industry having inherent but inhibited toxicity, no substantial percentage of fractions boiling below 270 C. and with in excess of 30% residual matter above 355 C. is heat treated in the liquid phase in'the presence of a hydrogen containing gas at a temperature selected' between the limits of 425500 C. whilst under apressure of 2,000 pounds for such a length of time as to jointly provide more than 10% but less than 50% newly formed materials boiling below 210 C., and a specific gravity of materials of cyclic structure content, as for example aromatics, in fractional parts of the beneficiated oil falling between the limits noted in the following tabular data: V

Fractions Low limit High limit and preferably between the limits noted below:

Fractions Low limit High limit 210-2a5 o 0. 041 1.0430 235-270" 0 0. 903 1.0000 270-315 0 1.001 1.0783 3l5355 o 1. 055 1.1135

When processing the named oil at the stated pressure and a temperature of 460 C., a period of about one hour and 15 minutes will illustratively provide a specific gravity of materials of cyclic structure content, as for example aromatics, in fractional parts of the beneficiated oil fallingbetween the stated preferred limits.

Upon inspection it is determined that the beneficiated material requires a smaller percentage for Ia given growth inhibition of wood destroying fungi than the crude starting stock.

- within limits. Unless the lower limit is approximated, toxicity induction is sacrificed. If the high limit is exceeded adverse reactions will occur that are conducive to inordinate gasiflcation,

inordinate production of fugitive materials of relatively low toxic value and/or polymerized products having objectionable characteristics. I

Various catalysts assist in the reforming, transforming, modifying and/or converting of the starting petroleum oils whereby to provide materials of induced toxic properties; These mcatalysts are employable either in the material remaining liquid under process controls, or in the evolved vapors, or both. Among such catalysts may be mentioned the various metals, their oxides, sulfides and carbonates; cellulosic materials and carbon, activated or otherwise. Various siliceous materials including the various clays shaped in appropriate form may also be employed. Various synthetic gels, as for instance.

the well known hydrogels, may also be employed "as .catalyticmaterials including specifically gelatinous precipitates properly prepared, Also employable as catalytic materials are halogens, halides and derivatives thereof including specifically substitution and addition products thereof, as for example and specifically substitution and addition products of said derivatives, say a hydrogen halid.

The temperatures of the instant process are selected between the limits of 350550 0., and preferably between 425-500 C. The pressures employed in the instant process are in excess of atmospheric and are specifically those pressures required for operation in the liquid phase. The

I striction, subjecting the highest boiling cut to the lowest temperature, etc.

In the examples shown in the foregoing, one or more phases, etc. of one example may be added to or substituted for other phase or phases in another example where the substitution or addition is obviously workable.

The evaluation of the materials of cyclic structure content and/or aromatics referred to in the foregoing is secured by recourse to the method disclosed under the caption .Neutral oils of coal hydrogenation-action of sulfuric, acid Indus-v trial and Engineering Bhemistry, volume 32, page 1614 et seq., December, 1940. H

Many modes of practicing the instant process are possible. As for example the oils of inherent but inhibited toxicity mentioned in the foregoing may be subjected to a destructive distillation under pressure and toxicity induced therein. The following disclosures will enable those skilled. in

J the art to practice such a process, and'at the same time adding details which will immediately 1 suggest themselves as routine and non-inventive improvements.

If desired, a mixture of petroleum fractions characterized by cyclic content, as for example the Shell product shown in the foregoing tabular data, having inherent but inhibited toxicity is charged to a still adapted to operate at superatmospheric pressure which communicates with a condenser. Intermediate the still and the condenser is an appropriate needle valve adapted to regulate the pressure within the still due. to the pressure of "evolved vapors. The still is so ar ranged that evolved vapors are at least partially refluxed. The reflux ratio may vary over wide limits and different efiects flow from varying percentages of reflux. Air is excluded from the still during the preliminary heating period and the needle valve then closed so as to develop the desired pressure within the still due to the pres sure of evolved vapors. The needle valveisthen partially. opened, and the valve aperture, heat control and reflux so coordinated as toprovide a relatively constant flow of evolved. vapors through the needle valve aperture.

Operating at a pressure of, as an example, a few hundred pounds or higher,.it is found that the oil under distillation is reformed, transformed, modified and/or converted and toxicity induced therein. It is also found that the temperature necessary for the distillation of any given percentage of the feed stock is considerably higher than for the distillation of a comparable percentage under substantially atmospheric pressure.

As the distillation proceeds the temperature is constant flow of distillate. The distillation is carried to the desired extent, as for example for the distillation reforming of or more of the feed stock, or the distillation may be carried to the greatest extent possible.

The time necessary for the distillation of a given charging stock will be determined by the speed of firing, percentage of reflux, etc., and the process may be ilustrated by recovering 3-10% of the 'still charge per hour as materials of induced toxic properties.

If desired, the distillate may be redistilled under similar destructive distillation conditions to provide additional toxic properties.

Hydrogen, hydrogen containing gases, materials yielding hydrogen, a or hydrocarbon gases may be employed within the still during the destructive distillation operation.

Minor changes within the scope of the appended claims may be made without departing from the spirit of the invention.

We claim: 1

1. As a preservative wood impregnant a. reformed petroleum oil boiling preponderantly between 210 C. and 355 0., having an end point at least as high as about 355 C. and substantial residual materials boiling above 315 C., the 210-235 C. fraction of which has an overall specific gravity between 0.801 and 1.0048, said fraction containing materials of ring structure content which have a specific gravity between 0.914 and 1.0580; the fraction 235270 C. of which has an overall specific gravity between 0.850 and' 1.0315 said fraction containing materials of ring structure content which have a specific gravity between 0.935 and 1.0756; the fraction 270-315 C.

of which hasan overall specific gravity between 0.914 and 1.0691, said fraction containing mate- 270 C. fraction of which has an overall specific gravity between 0.850 and 1.0315; said fraction containing materialsof ring structure content which have a specific gravity between 0.935 and 1.0756; the traction 270-315 C. of which has an overall specific gravity between 0.914 and 1.0691, said fraction containing materials of ring structure content which have a specific gravity between 0.97 3 and 1.0933; and the fraction of which boiling between 315 C. and 355 C. has an overall specific gravity between 0.973 and 1.1175, said fraction containing materials of ring structure content which have a specific gravity between 1.027 and 1.1285.

3. As a preservative wood impregnant a reformed petroleum oil boiling preponderantly between 210 C. and 355 0., having an end point at least as high as about 355 C. and substantial residual materials boiling above 315 C., the 270- 315 C. fraction of which has an overall specific gravity between 0.914 and 1.0691, said fraction containing materials of ring structure content which have a specific gravity between 0.973 and 1.0933.

4. As a preservative wood impregnant a reformed petroleum oil boiling preponderantly between 210 C. and 355 0., having an end point at least as high as about 355 C. and substantial residual materials boiling above 315 C., the 270- 315 C. fraction of which has an overall specific gravity between 0.914 and 1.0691, said fraction containing materials of ring structure content which have a specific gravity between 0.973 and 1.0933; and the fraction of which boiling between 315 C. and 355 C. has an overall specific gravity between 0.973 and 1.1175, said fraction containing materials of ring structure content which have a specific gravity between 1.027 and 1.1285.

JACQUELIN E. HARVEY, J 3. ROBERT H. WHITE, JR. JOSEPH A. VAUGHAN. 

